Ionic polyimide materials and methods of use

ABSTRACT

Disclosed are compositions and methods of preparing ionic polyimides. Also disclosed are methods to tune the properties of the ionic polyimide by designing the components of the ionic polyimide. Additionally, disclosed herein is a composition comprising an ionic polyimide. Also disclosed herein is a composition comprising an ionic polyimide and an ionic liquid. The disclosed compositions can be utilized to capture gases.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. ProvisionalApplication 62/098,068, filed Dec. 30, 2014, which is incorporated byreference herein in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

This invention was made with government support under grant numberCBET-1159397 awarded by the National Science Foundation. The governmenthas certain rights in the invention.

FIELD

The subject matter disclosed herein generally relates to ionicpolyimides, methods for the synthesis of ionic polyimides, and uses ofcompositions of ionic polyimides, e.g., to capture carbon dioxide.

BACKGROUND

Based on the growing concerns of the impact of rising levels ofgreenhouse gases (GHGs), there has been a great emphasis on developingstrategies to capture carbon dioxide to help curb emissions. Currenttechnology uses aqueous amines, such as monoethanolamine (MEA), tocapture carbon dioxide (CO₂). However, aqueous amines can suffer frommany deficiencies including amine degradation and solvent evaporation.Carbon dioxide (CO₂) can also be captured by a number of other methods,including using ionic liquids. Methods have been previously developed toseparate CO₂ from air utilizing ionic liquids based on the highdissolution rate of CO₂ into ionic liquids. The ionic liquid can alsoserve as an excellent solvent environment for amines. Additionally,methods have been developed to design ionic liquids to chemically bondwith CO₂ by tethering amines to one of the ionic components of an ionicliquid (see Bara et al., Acc. Chem. Res. 43 (2010) 152-159). While thesematerials and methods show great promise in certain applications, theycan be limited in other applications, e.g., when high temperaturesand/or reactive chemicals are involved. Thus what are needed are newmaterials than can be used to capture carbon dioxide under hightemperature or other specialized conditions. The materials and methodsdisclosed herein address these and other needs.

SUMMARY

The present disclosure generally relates to ionic polyimides and methodsfor the synthesis of ionic polyimides. In some aspects, the disclosedsynthetic methods can comprise a designable approach, which can allowfor a greater degree of control of the structure of the ionic polyimide.In some aspects, a dianhydride can be reacted with an amine attached toan ionizable heteroaryl. The heteroaryl can then be ionized through analkylation reaction with a molecule comprising at least two leavinggroups, which can generate a polymer.

In some aspects, a dianhydride can be reacted with an amine attached toa leaving group. The leaving group can then be reacted with an ionizableheteroaryl. The ionizable heteroaryl can then be ionized through analkylation reactions with a molecule comprising at least two leavinggroups, which can generate a polymer.

Also, disclosed herein are compositions comprising an ionic polyimide.Also disclosed herein are compositions comprising an ionic polyimide andan ionic liquid. The disclosed compositions can be utilized to capturegases and methods involving such uses are disclosed herein.

Additional advantages of the disclosed compositions and methods will beset forth in part in the description which follows, and in part will beobvious from the description. The advantages of the disclosedcompositions will be realized and attained by means of the elements andcombinations particularly pointed out in the appended claims. It is tobe understood that both the foregoing general description and thefollowing detailed description are exemplary and explanatory only andare not restrictive of the disclosed compositions, as claimed.

BRIEF DESCRIPTION OF THE FIGURE

The accompanying FIGURE, which is incorporated in and constitutes a partof this specification, illustrates several aspects described below.

FIG. 1 contains photographs of ionic polyimide films neat (left, top)and with ˜25 wt % “free” ionic liquid (IL) [C₂ mim][Tf₂N] content (left,bottom). The difference in optical clarity when “free” IL is presentillustrated by the pictures on right (top: without IL) and (bottom: withIL present).

DETAILED DESCRIPTION

Provided herein are methods for synthesizing ionic polyimides, which canbe designable in structure and function. Incorporating an ionicfunctionality can improve CO₂ absorption. Additionally, incorporatingionic functionality can allow for a tunable structure, chemicalproperties, and physical properties of the resulting ionic polyimidepolymer. The disclosed methods of synthesizing an ionic polyimide canallow for the synthesis of new structures of polyimides. Ionicpolyimides prepared by these methods, and compositions comprising suchionic polyimides (e.g., with ionic liquids) are also disclosed.

The materials, compounds, compositions, articles, and methods describedherein can be understood more readily by reference to the followingdetailed description of specific aspects of the disclosed subject matterand the Examples and Figures included therein.

Before the present materials, compounds, compositions, articles,devices, and methods are disclosed and described, it is to be understoodthat the aspects described below are not limited to specific syntheticmethods or specific reagents, as such may, of course, vary. It is alsoto be understood that the terminology used herein is for the purpose ofdescribing particular aspects only and is not intended to be limiting.

Also, throughout this specification, various publications arereferenced. The disclosures of these publications in their entiretiesare hereby incorporated by reference into this application in order tomore fully describe the state of the art to which the disclosed matterpertains. The references disclosed are also individually andspecifically incorporated by reference herein for the material containedin them that is discussed in the sentence in which the reference isrelied upon.

GENERAL DEFINITIONS

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings:

Throughout the description and claims of this specification the word“comprise” and other forms of the word, such as “comprising” and“comprises,” means including but not limited to, and is not intended toexclude, for example, other additives, components, integers, or steps.

As used in the description and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a composition”includes mixtures of two or more such compositions, reference to “anionic liquid” includes mixtures of two or more such ionic liquids,reference to “the compound” includes mixtures of two or more suchcompounds, and the like.

“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event or circumstance occurs and instances where itdoes not.

Ranges can be expressed herein as from “about” one particular value,and/or to “about” another particular value. When such a range isexpressed, another aspect includes from the one particular value and/orto the other particular value. Similarly, when values are expressed asapproximations, by use of the antecedent “about,” it will be understoodthat the particular value forms another aspect. It will be furtherunderstood that the endpoints of each of the ranges are significant bothin relation to the other endpoint, and independently of the otherendpoint. It is also understood that there are a number of valuesdisclosed herein, and that each value is also herein disclosed as“about” that particular value in addition to the value itself. Forexample, if the value “10” is disclosed, then “about 10” is alsodisclosed.

It is understood that throughout this specification the identifiers“first” and “second” are used solely to aid in distinguishing thevarious components and steps of the disclosed subject matter. Theidentifiers “first” and “second” are not intended to imply anyparticular order, amount, preference, or importance to the components orsteps modified by these terms.

CHEMICAL DEFINITIONS

A weight percent (wt. %) of a component, unless specifically stated tothe contrary, is based on the total weight of the formulation orcomposition in which the component is included.

The term “ion,” as used herein, refers to any molecule, portion of amolecule, cluster of molecules, molecular complex, moiety, or atom thatcontains a charge (positive, negative, or both at the same time withinone molecule, cluster of molecules, molecular complex, or moiety (e.g.,Zwitterions)) or that can be made to contain a charge. Methods forproducing a charge in a molecule, portion of a molecule, cluster ofmolecules, molecular complex, moiety, or atom are disclosed herein andcan be accomplished by methods known in the art, e.g., protonation,deprotonation, oxidation, reduction, alkylation acetylation,esterification, de-esterification, hydrolysis, etc.

The term “anion” is a type of ion and is included within the meaning ofthe term “ion.” An “anion” is any molecule, portion of a molecule (e.g.,Zwitterion), cluster of molecules, molecular complex, moiety, or atomthat contains a net negative charge or that can be made to contain a netnegative charge. The term “anion precursor” is used herein tospecifically refer to a molecule that can be converted to an anion via achemical reaction (e.g., deprotonation).

The term “cation” is a type of ion and is included within the meaning ofthe term “ion.” A “cation” is any molecule, portion of a molecule (e.g.,Zwitterion), cluster of molecules, molecular complex, moiety, or atom,that contains a net positive charge or that can be made to contain a netpositive charge. The term “cation precursor” is used herein tospecifically refer to a molecule that can be converted to a cation via achemical reaction (e.g., protonation or alkylation).

As used herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, and aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described below. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this disclosure, the heteroatoms, such as nitrogen, canhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valencies of theheteroatoms. This disclosure is not intended to be limited in any mannerby the permissible substituents of organic compounds. Also, the terms“substitution” or “substituted with” include the implicit proviso thatsuch substitution is in accordance with permitted valence of thesubstituted atom and the substituent, and that the substitution resultsin a stable compound, e.g., a compound that does not spontaneouslyundergo transformation such as by rearrangement, cyclization,elimination, etc. In specific examples, when a moiety is indicated asbeing substituted herein, it can be substituted with one or more groupsincluding, but not limited to, alkyl, halogenated alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid,ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo,sulfonyl, sulfone, sulfoxide, or thiol groups.

“A¹,” “A²,” and “A³,” are used herein as generic symbols to representvarious specific substituents. These symbols can be any substituent, notlimited to those disclosed herein, and when they are defined to becertain substituents in one instance, they can, in another instance, bedefined as some other substituents.

The term “aliphatic” as used herein refers to a non-aromatic hydrocarbongroup and includes branched and unbranched, alkyl, alkenyl, or alkynylgroups.

The term “alkyl” as used herein is a branched or unbranched saturatedhydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl,tetracosyl, and the like. The alkyl group can also be substituted orunsubstituted. The alkyl group can be substituted with one or moregroups including, but not limited to, alkyl, halogenated alkyl, alkoxy,alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid,ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo,sulfonyl, sulfone, sulfoxide, or thiol, as described below.

Throughout the specification “alkyl” is generally used to refer to bothunsubstituted alkyl groups and substituted alkyl groups; however,substituted alkyl groups are also specifically referred to herein byidentifying the specific substituent(s) on the alkyl group. For example,the term “halogenated alkyl” specifically refers to an alkyl group thatis substituted with one or more halide, e.g., fluorine, chlorine,bromine, or iodine. The term “alkoxyalkyl” specifically refers to analkyl group that is substituted with one or more alkoxy groups, asdescribed below. The term “alkylamino” specifically refers to an alkylgroup that is substituted with one or more amino groups, as describedbelow, and the like. When “alkyl” is used in one instance and a specificterm such as “alkyl alcohol” is used in another, it is not meant toimply that the term “alkyl” does not also refer to specific terms suchas “alkyl alcohol” and the like.

This practice is also used for other groups described herein. That is,while a term such as “cycloalkyl” refers to both unsubstituted andsubstituted cycloalkyl moieties, the substituted moieties can, inaddition, be specifically identified herein; for example, a particularsubstituted cycloalkyl can be referred to as, e.g., an“alkylcycloalkyl.” Similarly, a substituted alkoxy can be specificallyreferred to as, e.g., a “halogenated alkoxy,” a particular substitutedalkenyl can be, e.g., an “alkenylalcohol,” and the like. Again, thepractice of using a general term, such as “cycloalkyl,” and a specificterm, such as “alkylcycloalkyl,” is not meant to imply that the generalterm does not also include the specific term.

The term “alkenyl” as used herein is a hydrocarbon group of from 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon double bond. Asymmetric structures such as (A¹A²)C═C(A³A⁴)are intended to include both the E and Z isomers. This can be presumedin structural formulae herein wherein an asymmetric alkene is present,or it can be explicitly indicated by the bond symbol C═C. The alkenylgroup can be substituted with one or more groups including, but notlimited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl,heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide,or thiol, as described below.

The term “alkynyl” as used herein is a hydrocarbon group of 2 to 24carbon atoms with a structural formula containing at least onecarbon-carbon triple bond. The alkynyl group can be substituted with oneor more groups including, but not limited to, alkyl, halogenated alkyl,alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylicacid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo,sulfonyl, sulfone, sulfoxide, or thiol, as described below.

The term “aryl” as used herein is a group that contains any carbon-basedaromatic group including, but not limited to, benzene, naphthalene,phenyl, biphenyl, phenoxybenzene, triptycene, and the like. The term“heteroaryl” is defined as a group that contains an aromatic group thathas at least one heteroatom incorporated within the ring of the aromaticgroup. Examples of heteroatoms include, but are not limited to,nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term“non-heteroaryl,” which is also included in the term “aryl,” defines agroup that contains an aromatic group that does not contain aheteroatom. The aryl or heteroaryl group can be substituted orunsubstituted. The aryl or heteroaryl group can be substituted with oneor more groups including, but not limited to, alkyl, halogenated alkyl,alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylicacid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo,sulfonyl, sulfone, sulfoxide, or thiol as described herein. The term“biaryl” is a specific type of aryl group and is included in thedefinition of aryl. Biaryl refers to two aryl groups that are boundtogether via a fused ring structure, as in naphthalene, or are attachedvia one or more carbon-carbon bonds, as in biphenyl.

The term “cycloalkyl” as used herein is a non-aromatic carbon-based ringcomposed of at least three carbon atoms. Examples of cycloalkyl groupsinclude, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, etc. The term “heterocycloalkyl” is a cycloalkyl group whereat least one of the carbon atoms of the ring is substituted with aheteroatom such as, but not limited to, nitrogen, oxygen, sulfur, orphosphorus. The cycloalkyl group and heterocycloalkyl group can besubstituted or unsubstituted. The cycloalkyl group and heterocycloalkylgroup can be substituted with one or more groups including, but notlimited to, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde,amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro,silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as describedherein.

The term “cycloalkenyl” as used herein is a non-aromatic carbon-basedring composed of at least three carbon atoms and containing at least onedouble bound, i.e., C═C. Examples of cycloalkenyl groups include, butare not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like. The term“heterocycloalkenyl” is a type of cycloalkenyl group where at least oneof the carbon atoms of the ring is substituted with a heteroatom suchas, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Thecycloalkenyl group and heterocycloalkenyl group can be substituted orunsubstituted. The cycloalkenyl group and heterocycloalkenyl group canbe substituted with one or more groups including, but not limited to,alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino,carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl,sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol as described herein.

The term “cyclic group” is used herein to refer to either aryl groups,non-aryl groups (i.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, andheterocycloalkenyl groups), or both. Cyclic groups have one or more ringsystems that can be substituted or unsubstituted. A cyclic group cancontain one or more aryl groups, one or more non-aryl groups, or one ormore aryl groups and one or more non-aryl groups.

The term “aldehyde” as used herein is represented by the formula —C(O)H.Throughout this specification “C(O)” is a short hand notation for C═O.

The terms “amine” or “amino” as used herein are represented by theformula NA¹A²A³, where A¹, A², and A³ can be, independently, hydrogen,an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl groupdescribed above.

The term “carboxylic acid” as used herein is represented by the formula—C(O)OH. A “carboxylate” as used herein is represented by the formula—C(O)O⁻.

The term “ester” as used herein is represented by the formula —OC(O)A¹or —C(O)OA¹, where A¹ can be an alkyl, halogenated alkyl, alkenyl,alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl,or heterocycloalkenyl group described above.The term “ether” as used herein is represented by the formula A¹OA²,where A¹ and A² can be, independently, an alkyl, halogenated alkyl,alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,heterocycloalkyl, or heterocycloalkenyl group described above.The term “ketone” as used herein is represented by the formula A¹C(O)A²,where A¹ and A² can be, independently, an alkyl, halogenated alkyl,alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl,heterocycloalkyl, or heterocycloalkenyl group described above.The term “halide” as used herein refers to the halogens fluorine,chlorine, bromine, and iodine.

The term “hydroxyl” as used herein is represented by the formula —OH.

The term “nitro” as used herein is represented by the formula —NO₂.

The term “silyl” as used herein is represented by the formula —SiA¹A²A³,where A¹, A², and A³ can be, independently, hydrogen, alkyl, halogenatedalkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl,cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group describedabove.

The term “anhydride” as used herein is represented by the formula-A¹-C(O)OC(O)-A², where A¹ and A² can be, independently, hydrogen,alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl groupdescribed above.

“A¹,” “A²,” “A³,” “A^(n),” etc., where n is some integer, as used hereincan, independently, possess one or more of the groups listed above. Forexample, if A¹ is a straight chain alkyl group, one of the hydrogenatoms of the alkyl group can optionally be substituted with a hydroxylgroup, an alkoxy group, an amine group, an alkyl group, a halide, andthe like. Depending upon the groups that are selected, a first group canbe incorporated within second group or, alternatively, the first groupcan be pendant (i.e., attached) to the second group. For example, withthe phrase “an alkyl group comprising an amino group,” the amino groupcan be incorporated within the backbone of the alkyl group.Alternatively, the amino group can be attached to the backbone of thealkyl group. The nature of the group(s) that is (are) selected willdetermine if the first group is embedded or attached to the secondgroup.

As used herein, substantially pure means sufficiently homogeneous toappear free of readily detectable impurities as determined by standardmethods of analysis, such as thin layer chromatography (TLC), nuclearmagnetic resonance (NMR), gel electrophoresis, high performance liquidchromatography (HPLC) and mass spectrometry (MS), gas-chromatographymass spectrometry (GC-MS), and similar, used by those of skill in theart to assess such purity, or sufficiently pure such that furtherpurification would not detectably alter the physical and chemicalproperties, such as enzymatic and biological activities, of the subs

Materials and Compositions

Certain materials, compounds, compositions, and components disclosedherein can be obtained commercially or readily synthesized usingtechniques generally known to those of skill in the art. For example,the starting materials and reagents used in preparing the disclosedcompounds and compositions are either available from commercialsuppliers such as Aldrich Chemical Co., (Milwaukee, Wis.), AcrosOrganics (Morris Plains, N.J.), Fisher Scientific (Pittsburgh, Pa.),Sigma (St. Louis, Mo.), or are prepared by methods known to thoseskilled in the art following procedures set forth in references such asFieser and Fieser's Reagents for Organic Synthesis, Volumes 1-17 (JohnWiley and Sons, 1991); Rodd's Chemistry of Carbon Compounds, Volumes 1-5and Supplementals (Elsevier Science Publishers, 1989); OrganicReactions, Volumes 1-40 (John Wiley and Sons, 1991); March's AdvancedOrganic Chemistry, (John Wiley and Sons, 4th Edition); and Larock'sComprehensive Organic Transformations (VCH Publishers Inc., 1989). Othermaterials, such as the ligands, disclosed herein can be obtained fromcommercial sources.

Ionic Polyimides

One class of polymers that has been utilized previously for its highthermal stability and low chemical reactivity is polyimides. Polyimidesare polymers comprising repeating imide monomers. The primary method forthe synthesis of polyimides has been through a two-step reaction betweendianhydrides and diamines as seen in Scheme 1, which represents acondensation reaction. (See Scroog, Prog. Polym. Sci. 16 (1991)561-694.)

One challenge with polyimide design is that it is limited to the designof either one of the two starting components: the dianhydride or thediamine. Thus, only the molecular structure between the two aminefunctional groups or between the two anhydride functional groups can bealtered to change the properties of the polyimide.

Disclosed herein are methods to design a greater range of polyimidesthat can be utilized for carbon capture, in high temperatureapplications, and as lubricants, among other uses. By incorporatingionic functionality, an additional level of structural and spatialcontrol can be implemented to potentially improve CO₂ capture, themechanical properties, or the chemical properties of the polyimides.

Polyimides can be desirable for gas separation membranes due their highgas permeability, intrinsic selectivity and potentially desirablephysical properties. Polyimides such as MATRIMID™ and KAPTON™ weredeveloped for use in microelectronics and as thermal insulators. Whollyaromatic polyimides such as these can be synthesized via an initialcondensation of a diamine with a dianhydride at near ambienttemperature, followed by thermal imidization at higher temperature.MATRIMID™ and UPILEX™ can be useful for gas separations in commercialgas separation applications (e.g. H₂/CH₄, CO₂/CH₄, O₂/N₂, etc.) based ontheir ability to be processed into high quality films and fibers, eventhough their CO₂ permeabilities tend to be less than 20 Barrer, and wellbelow Robeson's Upper Bounds.

Recent developments in polyimide design have revolved around the use ofthe fluorinated dianhydride, 6-FDA, with bulky aromatic diamines. Thesematerials have can have higher CO₂ permeabilities (500-700 Barrer) dueto the large disruptions in chain packing (and increased FFV) caused by—CF₃ groups and multiple —CH₃ groups present on aromatic diamines suchas durene diamine. The inclusion of very bulky triptycene linkageswithin the polyimide backbone can increase the performance of polyimideswith CO₂ permeabilities approaching 3000 Barrers having been reportedvery recently (see Swaidan et al., Macomolecules 47 (2014) 5104-14).

Although seemingly two disparate classes of materials, ionic liquids(ILs) and rigid polyimides are integrated herein, resulting in so calledionic polyimides. Furthermore, the ionic polyimides can be more than thesum of their parts—rigid ionic polyimides can form unique, orderednanostructures that are not present in either of the parent materials.

In specific aspects, disclosed herein are ionic polyimides andcompositions thereof. In some examples the ionic polyimides can berepresented by Formula I:

wherein each dotted line represents an optional bond;

-   Y is null, H, halogen, OH, CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂,    NHR¹¹, CN, CR¹¹, CHR¹¹, CR¹¹ ₂, OR¹¹, C(CF₃)₂;-   Z is CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂, NHR¹¹, CN, CR¹¹, CHR¹¹,    CR¹¹ ₂, OR¹¹, substituted or unsubstituted C₁₋₂₀ alkyl, substituted    or unsubstituted C₂₋₂₀ alkenyl, substituted or unsubstituted C₂₋₂₀    alkynyl, substituted or unsubstituted C₁₋₂₀ heteroalkyl, substituted    or unsubstituted C₂₋₂₀ heteroalkenyl, substituted or unsubstituted    C₂₋₂₀ heteroalkynyl, substituted or unsubstituted cycloalkyl,    substituted or unsubstituted heterocycloalkyl, substituted or    unsubstituted aryl, substituted or unsubstituted heteroaryl, or    mixtures thereof, wherein any of the substituted groups named can be    substituted with one or more of alkyl, halogen, alkoxyl, alkenyl,    alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,    ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl,    sulfone, sulfoxide, or thiol groups;-   each R¹¹ is, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   L¹ is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   L² is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   Q is substituted or unsubstituted pyrazolium, substituted or    unsubstituted pyridinium, substituted or unsubstituted pyrazinium,    substituted or unsubstituted pyrimidinium, substituted or    unsubstituted pryidazinium, substituted or unsubstituted    piperidinium, substituted or unsubstituted pyrrolidinium,    substituted or unsubstituted indolizinium, substituted or    unsubstituted isoindolium, substituted or unsubstituted indolium,    substituted or unsubstituted indazolium, substituted or    unsubstituted imidazolium, substituted or unsubstituted oxazolium,    substituted or unsubstituted triazolium, substituted or    unsubstituted tetrazolium, substituted or unsubstituted thiazolium,    substituted or unsubstituted purinium, substituted or unsubstituted    isoquinolinium, substituted or unsubstituted quinolinium,    substituted or unsubstituted phthalazinium, substituted or    unsubstituted quinooxalinium, substituted or unsubstituted    phenazinium, substituted or unsubstituted morpholininium, or    mixtures thereof, wherein any of the substituted groups named can be    substituted with one or more alkyl, halogen, alkoxyl, alkenyl,    alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,    ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl,    sulfone, sulfoxide, or thiol groups.-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer between 1 and 100,000. In certain examples, Z is    substituted or-   unsubstituted triptycene.

In specific examples of Formula I, L¹ is a branched or straight chainC₁-C₁₀ alkyl. In other specific examples of Formula I, Q isunsubstituted or substituted imidazolium. In other examples of FormulaI, L² is an unsubstituted or substituted aryl, branched or straightchain C₁-C₁₀ alkyl, or C₁-C₁₀ heteroalkyl.

The ionic polyimides disclosed herein can be divided into subclasses ofcompounds based on the atoms between the two imide functional groups.One subclass of ionic polyimides can be represented by Formula II-A:

-   wherein L¹ is null, CH₂, C(O), O, S, SO₂, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   L² is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   Q is substituted or unsubstituted pyrazolium, substituted or    unsubstituted pyridinium, substituted or unsubstituted pyrazinium,    substituted or unsubstituted pyrimidinium, substituted or    unsubstituted pryidazinium, substituted or unsubstituted    piperidinium, substituted or unsubstituted pyrrolidinium,    substituted or unsubstituted indolizinium, substituted or    unsubstituted isoindolium, substituted or unsubstituted indolium,    substituted or unsubstituted indazolium, substituted or    unsubstituted imidazolium, substituted or unsubstituted oxazolium,    substituted or unsubstituted triazolium, substituted or    unsubstituted tetrazolium, substituted or unsubstituted thiazolium,    substituted or unsubstituted purinium, substituted or unsubstituted    isoquinolinium, substituted or unsubstituted quinolinium,    substituted or unsubstituted phthalazinium, substituted or    unsubstituted quinooxalinium, substituted or unsubstituted    phenazinium, substituted or unsubstituted morpholininium, or    mixtures thereof, wherein any of the substituted groups named can be    substituted with one or more alkyl, halogen, alkoxyl, alkenyl,    alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,    ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl,    sulfone, sulfoxide, or thiol groups.-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer between 1 and 100,000.

In some examples, Q can be an unsubstituted or substituted imidazoliumfunctional group, which can be represented by Formula II-A-1:

-   wherein L¹ is null, CH₂, C(O), O, S, SO₂, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   L² is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   R¹, R², and R³ are, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer from 1 to 100,000.

In some examples L¹ can be an unsubstituted or substituted phenylfunctional group, which can be represented by Formula II-A-2:

-   wherein L² is null, CH₂, C(O), O, S, SO₂, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   Q is substituted or unsubstituted pyrazolium, substituted or    unsubstituted pyridinium, substituted or unsubstituted pyrazinium,    substituted or unsubstituted pyrimidinium, substituted or    unsubstituted pryidazinium, substituted or unsubstituted    piperidinium, substituted or unsubstituted pyrrolidinium,    substituted or unsubstituted indolizinium, substituted or    unsubstituted isoindolium, substituted or unsubstituted indolium,    substituted or unsubstituted indazolium, substituted or    unsubstituted imidazolium, substituted or unsubstituted oxazolium,    substituted or unsubstituted triazolium, substituted or    unsubstituted tetrazolium, substituted or unsubstituted thiazolium,    substituted or unsubstituted purinium, substituted or unsubstituted    isoquinolinium, substituted or unsubstituted quinolinium,    substituted or unsubstituted phthalazinium, substituted or    unsubstituted quinooxalinium, substituted or unsubstituted    phenazinium, substituted or unsubstituted morpholininium, or    mixtures thereof, wherein any of the substituted groups named can be    substituted with one or more alkyl, halogen, alkoxyl, alkenyl,    alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,    ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl,    sulfone, sulfoxide, or thiol groups.-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer from 1 to 100,000.

In some examples, Q can be an unsubstituted or substituted imidazoliumfunctional group, L¹ can be propyl, and L² can be derived from1,4-dichlorodurene, which can be represented by Formula II-B:

-   wherein R¹, R², and R³ are, independent of any other, H, substituted    or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups; and-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer from 1 to 100,000.

In some examples, Q can be an unsubstituted or substituted imidazoliumfunctional group, L¹ can be propyl, L² can be derived from1,4-dichlorodurene, R¹ can be methyl, R² can be methyl, R³ can bemethyl, and A can be bis(trifluoromethane)sulfonamide, which can berepresented by Formula II-C:

-   wherein n is an integer from 1 to 100,000.

One subclass of ionic polyimides can be represented by Formula III,wherein a functional group, B, bridges two phenyl functional groups:

-   wherein B is halogen, OH, CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂,    NHR¹¹, CN, CR¹¹, CHR¹¹, CR¹¹2, OR¹¹, or C(CF₃)₂;-   each R¹¹ is, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   L¹ is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   L² is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   Q is substituted or unsubstituted pyrazolium, substituted or    unsubstituted pyridinium, substituted or unsubstituted pyrazinium,    substituted or unsubstituted pyrimidinium, substituted or    unsubstituted pryidazinium, substituted or unsubstituted    piperidinium, substituted or unsubstituted pyrrolidinium,    substituted or unsubstituted indolizinium, substituted or    unsubstituted isoindolium, substituted or unsubstituted indolium,    substituted or unsubstituted indazolium, substituted or    unsubstituted imidazolium, substituted or unsubstituted oxazolium,    substituted or unsubstituted triazolium, substituted or    unsubstituted tetrazolium, substituted or unsubstituted thiazolium,    substituted or unsubstituted purinium, substituted or unsubstituted    isoquinolinium, substituted or unsubstituted quinolinium,    substituted or unsubstituted phthalazinium, substituted or    unsubstituted quinooxalinium, substituted or unsubstituted    phenazinium, substituted or unsubstituted morpholininium, or    mixtures thereof, wherein any of the substituted groups named can be    substituted with one or more alkyl, halogen, alkoxyl, alkenyl,    alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,    ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl,    sulfone, sulfoxide, or thiol groups.-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer between 1 and 100,000.

In some examples, Q can be an unsubstituted or substituted imidazoliumfunctional group, which can be represented by Formula III-A:

-   wherein B is halogen, OH, CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂,    NHR¹¹, CN, CR¹¹, CHR¹¹, CR¹¹ ₂, OR¹¹, or C(CF₃)₂;-   each R¹¹ is, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   each R¹, R², and R³ is, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   L¹ is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   L² is null, CH₂, C(O), O, S, SO₂, substituted or unsubstituted C₁₋₂₀    alkyl, substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or    unsubstituted C₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀    heteroalkyl, substituted or unsubstituted C₂₋₂₀ heteroalkenyl,    substituted or unsubstituted C₂₋₂₀ heteroalkynyl, substituted or    unsubstituted cycloalkyl, substituted or unsubstituted    heterocycloalkyl, substituted or unsubstituted aryl, substituted or    unsubstituted heteroaryl, or mixtures thereof, wherein any of the    substituted groups named can be substituted with one or more of    alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl,    aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy,    ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or    thiol groups;-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer between 1 and 100,000.

In some examples, Q can be an unsubstituted or substituted imidazoliumfunctional group, L¹ can be propyl, and L² can be derived from1,4-dichlorodurene, which can be represented by Formula III-B:

-   wherein B is halogen, OH, CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂,    NHR¹¹, CN, C R¹¹, CHR¹¹, CR¹¹2, OR¹¹, or C(CF₃)₂;-   each R¹¹ is, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   each R¹, R², and R³ are, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups; and-   A is chloride, bromide, iodide, nitrate, dicyanamide, acetate,    bis(trifluoromethane)sulfonamide, hexafluorophosphate,    tetrafluoroborate, sulfate, phosphate,    tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,    thiocyanide, mesylate, triflate, or tosylate.-   n is an integer from 1 to 100,000.

In some examples, Q can be an unsubstituted or substituted imidazoliumfunctional group, L¹ can be propyl, L² can be derived from1,4-dichlorodurene, R¹ can be methyl, R² can be methyl, R³ can bemethyl, and A can be bis(trifluoromethane)sulfonamide, which can berepresented by Formula III-C:

-   wherein B is halogen, OH, CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂,    NHR¹¹, CN, CR¹¹, CHR¹¹, CR^(ii)2, OR¹¹, or C(CF₃)₂;-   each R¹¹ is, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups; and-   n is an integer from 1 to 100,000.

In some examples, Q can be an unsubstituted or substituted imidazoliumfunctional group, L¹ can be propyl, L² can be derived from1,4-dichlorodurene, R¹ can be methyl, R² can be methyl, R³ can bemethyl, A can be bis(trifluoromethane)sulfonamide and B can be —C(CF₃)₂,which can be represented by Formula III-D:

-   wherein n is an integer from 1 to 100,000.

Synthesis of an Ionic Polyimide

Also, disclosed herein are methods for synthesizing an ionic polyimidecomprising an ionized heteroaryl. The methods disclosed herein compriseat least four components: (1) a dianhydride, (2) an amine tethered to anionizable heteroaryl, (3) an alkylating agent, and (4) an anion. In someaspects, the disclosed method can generate an ionic polyimide byreacting the amine tethered to an ionizable heteroaryl to generate abridging monomer. (See Scheme 10.) The bridging monomer can be reactedwith an alkylating reagent to generate a repeating pattern. The anioncan be optionally exchanged.

Dianhydride

A dianhydride can be utilized to generate an ionic polyimide. Adianhydride molecule comprises two anhydride functional groups. Themolecular structure between the two anhydride functional groups can bealtered to adjust the resulting ionic polyimide's properties, such asthermal stability, chemical reactivity, viscosity, and melting point,among other chemical and physical properties. For example, incorporatingan aryl functional group into the dianhydride functional group can leadto greater thermal stability based on the stacking of the pi systems asa polymer.

Some suitable examples of dianhydrides include, but are not limited to,Benzoquinonetetracarboxylic dianhydride (BQDA), Ethylenetetracarboxylicdianhydride (EDA), Naphthalenetetracarboxylic dianhydride (NDA),Pyromellitic dianhydride (PMDA), Dioxane tetraketone (DTK),3,3′,4,4′-Diphenylsulfone tetracarboxylic dianhydride (DSDA),3,3′,4,4′-Benzophenone tetracarboxylic dianhydride (BTDA),3,3′,4,4′-Biphenyl tetracarboxylic dianhydride (s-BPDA),2,2′-Bis-(3,4-Dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA),4,4′-Oxydiphthalic anhydride (ODPA), 4,4′, Bisphenol A dianhydride(BPADA), Hydroquinone diphthalic anhydride (HQDEA), TRIPDA, and PIMDA.Some of these examples are illustrated in Scheme 2. Although someexamples of the dianhydride component are given in Scheme 2, anydianhydride can be selected.

In some other examples, suitable dianhydrides that can be used in thedisclosed methods are represented by Formula IV:

-   wherein each dotted line represents an optional bond;-   Y is null, H, halogen, OH, CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂,    NHR¹¹, CN, CR¹¹, CHR¹¹, CR¹¹2, OR¹¹, C(CF₃)₂;-   Z is CH, CH₂, C(O), O, S, SO₂, N, NH, NH₂, NHR¹¹, CN, CR¹¹, CHR¹¹,    CR¹¹2, OR¹¹, substituted or unsubstituted C₁₋₂₀ alkyl, substituted    or unsubstituted C₂₋₂₀ alkenyl, substituted or unsubstituted C₂₋₂₀    alkynyl, substituted or unsubstituted C₁₋₂₀ heteroalkyl, substituted    or unsubstituted C₂₋₂₀ heteroalkenyl, substituted or unsubstituted    C₂₋₂₀ heteroalkynyl, substituted or unsubstituted cycloalkyl,    substituted or unsubstituted heterocycloalkyl, substituted or    unsubstituted aryl, substituted or unsubstituted heteroaryl,    substituted or unsubstituted triptycene, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   each R¹¹ is, independent of any other, H, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxy, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups.

In some examples, suitable dianhydrides that can be used in thedisclosed methods can be connected to a substituted or unsubstitutedtriptycene moiety, wherein each anhydride functional group is attachedto a phenyl functional group in the triptycene moiety.

Amine

The disclosed methods also use a monoamine. In previous syntheticstrategies, a diamine has been utilized. However, the reaction between adiamine and a dianhydride can cause polymerization. Instead, if amolecule with a single amine functional group is used, polymerization isdisfavored. A reaction between two molecules that comprise a monoamineand a dianhydride results in a monomer containing two imide functionalgroups. (See Scheme 10.) This monomer can act as a “bridge” between theionized groups.

Attached to the monoamine is a functional group that is capable ofionizing. One such class of compounds that can be ionized areheteroaryls. If the amine functional group is tethered to a heteroaryl,it provides a molecule that can generate an imide monomer while stillhaving the capability to be ionized. (See Scheme 3.)

In some examples, suitable amines that can be used in the disclosedmethods are represented by Formula V:

-   wherein L¹ is null, CH₂, C(O), O, S, SO₂, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups;-   Q is substituted or unsubstituted pyrazoles, substituted or    unsubstituted pyridines, substituted or unsubstituted pyrazines,    substituted or unsubstituted pyrimidines, substituted or    unsubstituted pryidazines, substituted or unsubstituted piperidines,    substituted or unsubstituted pyrrolidines, substituted or    unsubstituted indolizines, substituted or unsubstituted isoindoles,    substituted or unsubstituted indoles, substituted or unsubstituted    indazoles, substituted or unsubstituted imidazoles, substituted or    unsubstituted oxazoles, substituted or unsubstituted triazoles,    substituted or unsubstituted tetrazoles, substituted or    unsubstituted thiazoles, substituted or unsubstituted purines,    substituted or unsubstituted isoquinolines, substituted or    unsubstituted quinolines, substituted or unsubstituted phthalazines,    substituted or unsubstituted quinooxalines, substituted or    unsubstituted phenazines, substituted or unsubstituted    morpholinines, or mixtures thereof, wherein any of the substituted    groups named can be substituted with one or more alkyl, halogen,    alkoxyl, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino,    carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro,    silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups.

In some specific examples, L¹ is a polyether, polyester, or polyamide offrom 1-100 atoms in length.

Some suitable classes of monoamines are shown in Scheme 3. The monoaminecan be attached to a variety of heteroaryls, such as but not limited to,azoles, imidazoles, 1,2,3-triazoles, 1,2,4-triazoles, tetrazoles,pyridines, piperidines, pyrrolidines, and pyrazoles. The heteroaryls canbe substituted with one or more functional groups, such as alkyl,halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino,carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl,sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups.

The amine group can be directly attached to the heteroaryl or attachedby a bridge. The bridge can be attached to a heteroatom or any one ofthe carbon atoms on the heteroaryl. The resulting reaction between themonoamine and the dianhydride can generate a bridging monomer, which canbe polymerized through a reaction with an alkylating agent.

Two-Step Synthesis of Bridging Monomer

In some embodiments, an amine attached to a leaving group can react witha dianhydride to form an imide (Scheme 7). In some examples, suitableamines attached to a leaving group that can be used in the disclosedmethods are represented by Formula VI:

-   Wherein L¹ is null, CH₂, C(O), O, S, SO₂, substituted or    unsubstituted C₁₋₂₀ alkyl, substituted or unsubstituted C₂₋₂₀    alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substituted or    unsubstituted C₁₋₂₀ heteroalkyl, substituted or unsubstituted C₂₋₂₀    heteroalkenyl, substituted or unsubstituted C₂₋₂₀ heteroalkynyl,    substituted or unsubstituted cycloalkyl, substituted or    unsubstituted heterocycloalkyl, substituted or unsubstituted aryl,    substituted or unsubstituted heteroaryl, or mixtures thereof,    wherein any of the substituted groups named can be substituted with    one or more of alkyl, halogen, alkoxyl, alkenyl, alkynyl, aryl,    heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,    hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone,    sulfoxide, or thiol groups; and-   X is Cl, Br, I, O, O-Ph-SO₃CH₃, SO₃CH₃, or SO₃CH₃.

The leaving group, X can then react with an ionizable heteroaryl, Q, toform the bridging monomer, wherein Q is substituted or unsubstitutedpyrazoles, substituted or unsubstituted pyridines, substituted orunsubstituted pyrazines, substituted or unsubstituted pyrimidines,substituted or unsubstituted pryidazines, substituted or unsubstitutedpiperidines, substituted or unsubstituted pyrrolidines, substituted orunsubstituted indolizines, substituted or unsubstituted isoindoles,substituted or unsubstituted indoles, substituted or unsubstitutedindazoles, substituted or unsubstituted imidazoles, substituted orunsubstituted oxazoles, substituted or unsubstituted triazoles,substituted or unsubstituted tetrazoles, substituted or unsubstitutedthiazoles, substituted or unsubstituted purines, substituted orunsubstituted isoquinolines, substituted or unsubstituted quinolines,substituted or unsubstituted phthalazines, substituted or unsubstitutedquinooxalines, substituted or unsubstituted phenazines, substituted orunsubstituted morpholinines, or mixtures thereof, wherein any of thesubstituted groups named can be substituted with one or more alkyl,halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino,carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl,sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol groups.

Alkylating Agent

If the alkylating agent is capable of two alkyation reactions, thealkylating agent can serve to connect the bridging monomers into dimers,trimers, and ultimately a polymer. The growth of the polymer can resultfrom such a reaction as disclosed herein.

In some examples, suitable alkylating agents that can be used in thedisclosed methods are represented by Formula VII:

-   wherein L² is substituted or unsubstituted C₁₋₂₀ alkyl, substituted    or unsubstituted C₂₋₂₀ alkenyl, substituted or unsubstituted C₂₋₂₀    alkynyl, substituted or unsubstituted C₁₋₂₀ heteroalkyl, substituted    or unsubstituted C₂₋₂₀ heteroalkenyl, substituted or unsubstituted    C₂₋₂₀ heteroalkynyl, substituted or unsubstituted cycloalkyl,    substituted or unsubstituted heterocycloalkyl, substituted or    unsubstituted aryl, substituted or unsubstituted heteroaryl, or    mixtures thereof, wherein any of the substituted groups named can be    substituted with one or more of alkyl, halogen, alkoxyl, alkenyl,    alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester,    ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl,    sulfone, sulfoxide, or thiol groups; and-   X is Cl, Br, I, O, O-Ph-SO₃CH₃, SO₃CH₃, or SO₃CH₃.

Possible examples of suitable alkylating agents are show in Scheme 4. Insome aspects, the alkylating agent comprises at least two leavinggroups. Some leaving groups include, but are not limited to, chlorine,bromine, iodine, methanesulfonyl(mesylate),trifluoromethanesulfonyl(triflate), or p-toluenesuifonyl(tosylate). Asubstitution reaction can take place between the alkylating agent andthe ionizable heteroaryl as described above. This substitution reactioncan result in the heteroaryl reacting with the carbon atom directly nextto one of the leaving groups, which can result in a cationic heteroaryland the leaving group as an anion. The reaction between the alkylatingagent and the bridging monomer can generate an ionic polyimide. (SeeScheme 10.)

A suitable bridge can connect the two leaving groups. The bridge can beselected based on its impact on chemical or physical properties of theresulting polymer. The bridge can comprise alkyl, alkenyl, alkynyl,aryl, ether, or ester functionality. Some examples of suitable bridgescan be seen in Scheme 4.

Anions

The leaving groups can be used as an anion for the cationic monomer as abyproduct of the reaction between the alkylating agent and the bridgingmonomer. In some aspects, the anion can be exchanged for another anionthat can be improve properties, such as viscosity, CO₂ affinity, ormelting point. The anion can be exchanged by methods known to a personskilled in the art.

Some suitable anions that can be utilized can be seen in Scheme 5. Insome aspects the anion can be chloride, bromide, iodide, nitrate,dicyanamide, acetate, bis(trifluoromethane)sulfonamide,hexafluorophosphate, tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, or tosylate.

Synthesis of Ionic Polyimide

The disclosed methods for synthesizing an ionic polyimide can beillustrated by Scheme 10. The ionic polyimide can be synthesized by thecondensation reaction between a dianhydride (e.g., those shown in Scheme2) and a suitable monoamine (e.g., those shown in Scheme 3). Thereaction can be performed neat or in in a solvent. The reaction can beoptionally heated. After an optional removal of the solvent, theresulting molecule can be a bridging monomer comprising two imidefunctional groups and two ionizable heteroaryls. An alkylating agentwith at least two leaving groups (Scheme 4) can connect two monomers ofthe bridging monomer through a substitution reaction. This reaction cancreate a positively charged dimer, trimer, or polymer paired with asuitable anion (Scheme 5). This can represent a step-growthpolymerization method.

Condensation Reaction to form a Monomeric Imide

The ionic polyimide can be synthesized by a condensation reactionbetween a dianhydride (Scheme 2) and a suitable amine (Scheme 3). Asshown in Scheme 6, the dianhydride can be mixed with two molarequivalents of the amine attached to a heteroaryl in a suitable solvent.The amine functional group can react with the anhydride functional groupto form an imide functional group and a molecule of water, which can beremoved with the solvent. The resulting product is a bridging monomer.In previously developed methods (Scheme 1), utilizing a diamine, apolymer can be synthesized. However, disclosed herein is a method tosynthesize a bridging monomer, which can allow for greater structurecontrol before the step growth mechanism to synthesize a polymer.

Some suitable solvents include, but are not limited to water,dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, acetone,acetonitrile, N,N-dimethylformamide, or dimethyl sulfoxide. The reactioncan also be optionally heated up to 150° C.

The reaction mixture can be stirred and heated for up to 48 hours togenerate the bridging monomer. After the removal the solvent andgenerated water, the bridging monomer can be isolated.

The monomeric imide, or bridging monomer, can also be synthesized by amulti-step reaction. As seen in Scheme 7, the dianhydride can be mixedwith two molar equivalents of the amine attached to a leaving group in asuitable solvent. The amine functional group can react with theanhydride functional group to form an imide functional group and amolecule of water, which can be removed with the solvent. The resultingcompound can be reacted with two equivalents of heteroaryl to form thebridging monomer.

Some suitable solvents include, but are not limited to water,dichloromethane, chloroform, ethyl acetate, tetrahydrofuran, acetone,acetonitrile, N,N-dimethylformamide, or dimethyl sulfoxide. The reactioncan also be optionally heated up to 150° C.

The heteroaryl may be deprotonated to react with the imide attached to ahalogen. The reaction mixture can be stirred and heated for up to 48hours to generate the bridging monomer. After the removal the solventand generated water, the bridging monomer can be isolated.

Alkylation Reaction to Ionize the Heteroaryl

The synthesized bridging monomer can be ionized through an alkylationreaction with a suitable alkylating agent as described above (see e.g.,Scheme 4). The bridging monomer can be mixed with the alkylating agentin a suitable solvent. The attached heteroaryl can react with the carbonatom next to one of the leaving groups. This alkylation reaction canpositively ionize the bridging monomer and generate a negatively chargedanion from leaving group (Scheme 8). By selecting an alkylating agentwith at least two leaving groups connected by a suitable bridge asdescribed above, the alkylation reaction can result in the step-growthof a polymer. In some aspects the alkylation reaction forms a dimer,trimer, or a longer polymer.

Some suitable solvents include, but are not limited to water, methanol,ethanol, dichloromethane, chloroform, ethyl acetate, tetrahydrofuran,acetone, acetonitrile, N,N-dimethylformamide, or dimethyl sulfoxide. Thereaction can also be optionally heated up to 150° C.

The reaction mixture can be stirred and heated for up to 48 hours togenerate the alkylated polymer. A person skilled in the art would knowother conditions for the reaction.

After, the removal the solvent and generated water, the bridging ionicpolyimide can be isolated.

Optionally, a salt can be added to the alkylation reaction mixture tochange the identity of the anion (Scheme 9). For example, instead ofhaving the anionic version of the leaving group, the anion could beexchanged for another anion, such as but not limited to chloride,bromide, iodide, nitrate, dicyanamide, acetate,bis(trifluoromethane)sulfonamide, hexafluorophosphate,tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, or tosylate.

Metathesis Reaction

Instead of exchanging the anion during the alkylation reaction, theanion can also be optionally exchanged in a separate reaction after theend of the alkylation reaction. Mixing the ionic polyimide with a saltthat has a different anion can exchange one anion for another (Scheme10). For example, the anion could be exchanged for another anion, suchas but not limited to chloride, bromide, iodide, nitrate, dicyanamide,acetate, bis(trifluoromethane)sulfonamide, hexafluorophosphate,tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, or tosylate.

Some suitable solvents for the methathesis include, but are not limitedto water, methanol, ethanol, dichloromethane, chloroform, ethyl acetate,tetrahydrofuran, acetone, acetonitrile, N,N-dimethylformamide, ordimethyl sulfoxide. The reaction can also be optionally heated up to150° C.

The reaction mixture can be stirred and heated for up to 48 hours togenerate the alkylated polymer. A person skilled in the art would knowother conditions for the reaction. After the removal the solvent andgenerated water, the bridging ionic polyimide can be isolated.

Ionic Polyimide Design

The heteroaryl structures can been chosen to influence H-bonding byreducing/blocking or enhancing the ability of the heteroaryl ring toundergo these types of interactions. The components can be selected toform highly porous, structured architectures that can be translatable toionic polyimides formed with covalent bonds.

However, retention of helix structures in the final ionic polyimide canbe dependent on the use of a rigid linker group, such as para- ormeta-xylyl, cyclohexyl or similar structures that can provide additionalfrustrations to chain packing, i.e. the ionic polyimide must beconstructed based upon the same principles that have driven theperformance of conventional polyimides.

Finally, the selection of the anion can play a role in the overallstructure and supramolecular assembly of ionic polyimides. Based onanalogy to ILs and poly(ILs), halide anions can provide largerT_(g)/T_(m) values and stronger H-bonds than the molecular anions whichcan aid organization. However, molecular anions such as BF₄ and Tf₂N canstill exhibit these H-bonding interactions and can produce a moretractable polymer.

Compositions of Ionic Liquids

In some examples, an ionic polyimide can be mixed with an ionic liquid.Some suitable examples are provided herein.

In one aspect, disclosed herein are ionic liquid compositions. The term“ionic liquid” has many definitions in the art, but is used herein torefer to salts (i.e., compositions comprising cations and anions) thatare liquid at a temperature of at or below about 150° C., e.g., at orbelow about 120, 100, 80, 60, 40, or 25° C. That is, at one or moretemperature ranges or points at or below about 150° C. the disclosedionic liquid compositions are liquid; although, it is understood thatthey can be solids at other temperature ranges or points. Since thedisclosed ionic liquid compositions are liquid, and thus not crystallinesolids, at a given temperature, the disclosed compositions do not sufferfrom the problems of polymorphism associated with crystalline solids. Anionic liquid is not considered a mere solution containing ions assolutes dissolved therein.

The use of the term “liquid” to describe the disclosed ionic liquidcompositions is meant to describe a generally amorphous,non-crystalline, or semi-crystalline state. For example, while somestructured association and packing of cations and anions can occur atthe atomic level, the disclosed ionic liquid compositions have minoramounts of such ordered structures and are therefore not crystallinesolids. The compositions disclosed herein can be fluid and free-flowingliquids or amorphous solids such as glasses or waxes at a temperature ator below about 150° C. In particular, examples disclosed herein, thedisclosed ionic liquid compositions are liquid at which the compositionis applied (i.e., ambient temperature).

Further, the disclosed ionic liquid compositions are materials composedof at least two different ions; each of which can independently andsimultaneously introduce a specific characteristic to the compositionnot easily obtainable with traditional dissolution and formulationtechniques. Thus, by providing different ions and ion combinations, onecan change the characteristics or properties of the disclosed ionicliquid compositions in a way not seen by simply preparing variouscrystalline salt forms. Examples of characteristics that can becontrolled in the disclosed compositions include, but are not limitedto, melting, solubility control, and rate of dissolution. It is thismulti-nature/functionality of the disclosed ionic liquid compositionswhich allows one to fine-tune or design in very specific desiredmaterial properties.

It is further understood that the disclosed ionic liquid compositionscan include solvent molecules (e.g., water); however, these solventmolecules should not be present in excess in the sense that thedisclosed ionic liquid compositions are dissolved in the solvent,forming a solution. That is, the disclosed ionic liquid compositionscontain no or minimal amounts of solvent molecules that are free and notbound or associated with the ions present in the ionic liquidcomposition. Thus, the disclosed ionic liquid compositions can be liquidhydrates or solvates, but not solutions.

Ionic liquids have been of general interest because they areenvironmentally-friendly alternatives to organic solvents for variouschemical processes, e.g., liquid/liquid extractions, catalysis,separations, and electrochemistry. Ionic liquids have also becomepopular alternative media for chemical synthesis because of their lowvolatility and low toxicity. See e.g., Wasserscheid and Keim, Angew ChemInt Ed Engl, 2000, 39:3772; and Wasserscheid, “Ionic Liquids inSynthesis,” 1^(st) Ed., Wiley-VCH, 2002. Further, ionic liquids canreduce costs, disposal requirements, and hazards associated withvolatile organic compounds. Other exemplary properties of ionic liquidsare high ionic conductivity, non-volatility, non-flammability, highthermal stability, wide temperature for liquid phase, highlysolvability, and non-coordinating. For a review of ionic liquids see,for example, Welton, Chem Rev. 1999, 99:2071-2083; and Carlin et al.,Advances in Nonaqueous Chemistry, Mamantov et al. Eds., VCH Publishing,New York, 1994.

The specific physical properties (e.g., melting point, viscosity,density, water solubility, etc.) of ionic liquids are determined by thechoice of cation and anion, as is disclosed more fully herein. As anexample, the melting point for an ionic liquid can be changed by makingstructural modifications to the ions or by combining different ions.Similarly, the particular chemical properties (e.g., bioactivity,toxicity, pharmacokinetics, etc.), can be selected by changing theconstituent ions of the ionic liquid.

The disclosed ionic liquids care liquid at some temperature range orpoint at or below about 150° C. For example, the disclosed ionic liquidscan be a liquid at or below about 150, 149, 148, 147, 146, 145, 144,143, 142, 141, 140, 139, 138, 137, 136, 135, 134, 133, 132, 131, 130,129, 128, 127, 126, 125, 124, 123, 122, 121, 120, 119, 118, 117, 116,115, 114, 113, 112, 111, 110, 109, 108, 107, 106, 105, 104, 103, 102,101, 100, 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 89, 88, 87, 86, 85,84, 83, 82, 81, 80, 79, 78, 77, 76, 75, 74, 73, 72, 71, 70, 69, 68, 67,66, 65, 64, 63, 62, 61, 60, 59, 58, 57, 56, 55, 54, 53, 52, 51, 50, 49,48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31,30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13,12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0, −1, −2, −3, −4, −5, −6, −7,−8, −9, −10, −11, −12, −13, −14, −15, −16, −17, −18, −19, −20, −21, −22,−23, −24, −25, −26, −27, −28, −29, or −30° C., where any of the statedvalues can form an upper or lower endpoint when appropriate. In furtherexamples, the disclosed ionic liquids can be liquid at any point fromabout −30° C. to about 150° C., from about −20° C. to about 140° C.,−10° C. to about 130° C., from about 0° C. to about 120° C., from about10° C. to about 110° C., from about 20° C. to about 100° C., from about30° C. to about 90° C., from about 40° C. to about 80° C., from about50° C. to about 70° C., from about −30° C. to about 50° C., from about−30° C. to about 90° C., from about −30° C. to about 110° C., from about−30° C. to about 130° C., from about −30° C. to about 150° C., fromabout 30° C. to about 90° C., from about 30° C. to about 110° C., fromabout 30° C. to about 130° C., from about 30° C. to about 150° C., fromabout 0° C. to about 100° C., from about 0° C. to about 70° C., fromabout 0° to about 50° C., and the like.

Further, in some examples the disclosed ionic liquid compositions can beliquid over a wide range of temperatures, not just a narrow range of,say, 1-2 degrees. For example, the disclosed ionic liquid compositionscan be liquids over a range of at least about 4, 5, 6, 7, 8, 9, 10, ormore degrees. In other example, the disclosed ionic liquid compositionscan be liquid over at least about a 11, 12, 13, 14, 15, 16, 17, 18, 19,20, or more degree temperature range. Such temperature ranges can beginand/or end at any of the temperature points disclosed in the precedingparagraph.

In many examples disclosed herein the disclosed ionic liquidcompositions are liquid at the temperature at which they will be used orprocessed (e.g., ambient temperature). In still other examples, thedisclosed compositions can be liquid at the temperature at which theyare formulated or processed.

It is understood, however, that the disclosed ionic liquid compositionscan, though need not, be solubilized, and solutions of the disclosedionic liquids are contemplated herein. Further, the disclosed ionicliquid compositions can be formulated in an extended or controlledrelease vehicle, for example, by encapsulating the ionic liquids inmicrospheres or microcapsules using methods known in the art. Stillfurther, the disclosed ionic liquid compositions can themselves besolvents for other solutes. For example, the disclosed ionic liquids canbe used to dissolve a particular nonionic or ionic herbicidal active.These and other formulations of the disclosed ionic liquids aredisclosed elsewhere herein.

In some examples, the disclosed ionic liquids are not solutions whereions are dissolved in a solute. In other examples, the disclosed ionicliquid compositions do not contain ionic exchange resins. In still otherexamples, the disclosed ionic liquids are substantially free of water.By substantially free is meant that water is present at less than about10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.25, or 0.1 wt. %, based on thetotal weight of the composition.

Cations

Particular examples of cationic compounds that can be present in thedisclosed compositions are compounds that contain nitrogen or phosphorusatoms. Nitrogen atom-containing groups can exist as neutral or can beconverted to positively-charged quaternary ammonium species, forexample, through alkylation or protonation of the nitrogen atom. Thus,compounds that possess a quaternary nitrogen atom (known as quaternaryammonium compounds (QACs)) are typically cations. According to themethods and compositions disclosed herein, any compound that contains aquaternary nitrogen atom or a nitrogen atom that can be converted into aquaternary nitrogen atom can be a suitable cation for the disclosedcompositions. In some examples, the cation is not a protonated tertiaryamine, a protonated heteroarylamine, a protonated pyrrolidine, or ametal.

Some specific QACs suitable for use herein are aliphatic heteroaryls. Analiphatic heteroaryl cation is a compound that comprises at least onealiphatic moiety bonded to a heteroaryl moiety. In the aliphaticheteroaryl cation, the aliphatic moiety can be any alkyl, alkenyl,alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, cycloalkyl,cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group, asdescribed herein. For example, the aliphatic moiety can includesubstituted or unsubstituted C₁₋₂₀ alkyl, substituted or unsubstitutedC₂₋₂₀ alkenyl, substituted or unsubstituted C₂₋₂₀ alkynyl, substitutedor unsubstituted C₁₋₂₀ heteroalkylsubstituted or unsubstituted C₂₋₂₀heteroalkenyl, or substituted or unsubstituted C₂₋₂₀ heteroalkynylgroups. In the aliphatic heteroaryl cations, the aliphatic moiety isbonded to a heteroatom in the heteroaryl moiety.

In the aliphatic heteroaryl cation, the heteroaryl moiety can be anyheteroaryl moiety as described herein. For example, the heteroarylmoiety can be an aryl group having one or more heteroatoms (e.g.,nitrogen, oxygen, sulfur, phosphorous, or halonium). Examples ofspecific heteroaryl moieties that can be used in the aliphaticheteroaryl cations include, but are not limited to, substituted orunsubstituted pyrazoles, substituted or unsubstituted pyridines,substituted or unsubstituted pyrazines, substituted or unsubstitutedpyrimidines, substituted or unsubstituted pryidazines, substituted orunsubstituted indolizines, substituted or unsubstituted isoindoles,substituted or unsubstituted indoles, substituted or unsubstitutedindazoles, substituted or unsubstituted imidazoles, substituted orunsubstituted oxazoles, substituted or unsubstituted triazoles,substituted or unsubstituted thiazoles, substituted or unsubstitutedpurines, substituted or unsubstituted isoquinolines, substituted orunsubstituted quinolines, substituted or unsubstituted phthalazines,substituted or unsubstituted quinooxalines, substituted or unsubstitutedphenazine, and the like, including derivatives and mixtures thereof. Inthe aliphatic heteroaryl cations, a heteroatom in the heteroaryl moietyis bonded to the aliphatic moiety. When the heteroatom of the heteroarylis nitrogen, this forms a quaternary ammonium cation, as describedherein.

Further examples of aliphatic heteroaryl cations include substituted orunsubstituted benztriazoliums, substituted or unsubstitutedbenzimidazoliums, substituted or unsubstituted benzothiazoliums,substituted or unsubstituted pyridiniums, substituted or unsubstitutedpyridaziniums, substituted or unsubstituted pyrimidiniums, substitutedor unsubstituted pyraziniums, substituted or unsubstituted imidazoliums,substituted or unsubstituted pyrazoliums, substituted or unsubstitutedoxazoliums, substituted or unsubstituted 1,2,3-triazoliums, substitutedor unsubstituted 1,2,4-triazoliums, substituted or unsubstitutedthiazoliums, substituted or unsubstituted piperidiniums, substituted orunsubstituted pyrrolidiniums, substituted or unsubstituted quinoliums,and substituted or unsubstituted isoquinoliums.

Tetraalkyl Ammonium

The disclosed compositions can also comprise a tetraalkyl ammoniumcation. Suitable tetraalkyl ammonium cations comprise four alkylmoieties, as disclosed herein. In one example, a tetraalkyl ammoniumcation can comprise one long chain alkyl moiety (e.g., 10 or more carbonatoms in length) and three short chain alkyl moieties (e.g., less than10 carbon atoms in length).

Some specific examples of tetraalkyl ammonium cations that can beincluded in the disclosed compositions include, but are not limited to,cetyl trimethyl ammonium, lauryl trimethyl ammonium, myristyl trimethylammonium, stearyl trimethyl ammonium, arachidyl trimethyl ammonium, ormixtures thereof. Other examples include, but are not limited to, cetyldimethylethyl ammonium, lauryl dimethylethyl ammonium, myristyldimethylethyl ammonium, stearyl dimethylethyl ammonium, arachidyldimethylethyl ammonium, or mixtures thereof.

Anions

Some suitable anions include, but are not limited to, chloride, bromide,iodide, nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonamide,hexafluorophosphate, tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, or tosylate.

Compositions of Ionic Polyimides and Ionic Liquids

An additional dimension of control over material structure, propertiesand performance can be the introduction of “free” IL into the polymermatrix that can further serve to aid assembly via selective,non-covalent interactions with the ionic segments of the polymerbackbone. This concept has been applied to amorphous “side-chain”poly(ILs) and ionenes to improve CO₂ permeability compared to the neatpolymer material alone. Lodge and co-workers have successfully appliedsuch approaches to the self-assembly of linear block copolymerscontaining polar or ionic blocks within non-polar polystyrene blocks,with promising results for a CO₂ separation membrane. (See He et al., J.Am. Chem. Soc. 128 (2006) 2745-50.) However, although such polymermaterials exhibit improved performance when ILs are included in themembrane, they can be largely composed of a relatively impermeablepoly(styrene) component, can rely on radical polymerization mechanismsand can lack the unique folds and twists that can be imparted by somemolecules like 6-FDA. Thus the introduction of “free” ILs into ionicpolyimides can provide the driving force needed create highly open, yetordered nanostructures.

Gas Capture with Ionic Polyimides

Disclosed herein are methods to capture gases utilized disclosedcompositions. These compositions are useful for reducing volatilecompounds, such as carbon dioxide (CO₂), carbon monoxide (CO), sulfurdioxide (SO₂), hydrogen sulfide (H₂S), nitrogen oxide (NO), nitrogendioxide (NO₂), carbonyl sulfide (COS), and carbon disulfide (CS₂),mercaptans, H₂O, O₂, H₂, N₂, C₁-C₈ hydrocarbons (e.g., methane andpropane), volatile organic compounds, and mixtures of these and othervolatile compounds from gas streams and liquid streams.

Contacting a gas stream with a membrane comprising an ionic polyimidecan result in the absorption of volatile compounds. Contacting a gasstream with a membrane comprising an ionic polyimide and an ionic liquidcan result in the absorption of volatile compounds.

EXAMPLES

The following examples are set forth below to illustrate the methods andresults according to the disclosed subject matter. These examples arenot intended to be inclusive of all aspects of the subject matterdisclosed herein, but rather to illustrate representative methods andresults. These examples are not intended to exclude equivalents andvariations of the present invention, which are apparent to one skilledin the art.

Efforts have been made to ensure accuracy with respect to numbers (e.g.,amounts, temperature, etc.) but some errors and deviations should beaccounted for. Unless indicated otherwise, parts are parts by weight,temperature is in ° C. or is at ambient temperature, and pressure is ator near atmospheric. There are numerous variations and combinations ofreaction conditions, e.g., component concentrations, temperatures,pressures and other reaction ranges and conditions that can be used tooptimize the product purity and yield obtained from the describedprocess. Only reasonable and routine experimentation will be required tooptimize such process conditions.

All chemicals used were of analytical grade, purchased fromSigma-Aldrich (St. Louis, Mo.) or Alfa Aesar (Ward Hil, Mass.), and usedwithout further purification unless otherwise noted.

Example 1 Ionic Polyimide synthesized from1-(3-aminopropyl)-2,4,5-trimethylimidazole, 6-FDA and 1,4-dichlorodurene

2 equivalents of 1-(3-aminopropyl)-2,4,5-trimethylimidazole) can bemixed with 6-FDA in N,N-dimethylformamide. The reaction can be stirredfor 16 hours at 120° C., to generate a bridging monomer. An equivalentmolar ratio of alkylating agent and lithiumbis(trifluoromethane)sulfonimide. The composition can be stirred for anadditional 16 hours at 120° C. to generate an ionic polyimide (seeScheme 11).

Example 2 Ionic Polyimide synthesized from imidazole, p-bromoaniline,PMDA and α domdichloro-p-xylene

2 equivalents of p-bromoaniline can be reacted with PMDA indimethylformamide. The reaction can be stirred at 150° C. for 16 hours.The product is reacted with 2 equivalents of imidazole with cesiumcarbonate, copper iodide for an additional 48 hours in dimethylformamideat 150° C. to generate the bridging monomer. The bridging monomer can bealkylated with α,α″-dichloro-p-xylene in the presence of lithiumbis(trifluoromethane)sulfonimide in N-methyl-2-pyrrolidone at 150° C.for an additional 16 hours. The ionic polyimide can be separated fromthe reaction mixture.

Example 3 Pressing of an Ionic Polyimide into a Film for CO₂ Capture

Approximately 1.00 g of material was pressed at 220° C. into a thin filmof about 200 μm thickness and >60 mm in diameter. A 47 mm disc waspunched from the larger film and then tested in a time-lag membraneapparatus. The CO₂ permeability of this initial material was determinedto be relatively low (about 1 Barrer), and as such, other gases were nottested. The low permeability of CO₂ in the ionic polyimide described inExample 1 is not unexpected as PMDA is not typically employed inconventional aromatic polyimide materials due to its rigidity. InitialSEM and XRD characterization results show that the ionic polyimide basedon PMDA is relatively amorphous with some crystalline regions), which iscorrelated to the low permeability level observed in this firstmaterial.

Example 4 Pressing of an Ionic Polyimide with 25 wt. %1-ethyl-3-methylimidazolium bis(trifluoromethane)sulfonamide into a Filmfor CO₂ Capture

The ionic polyimide based on PMDA can directly interface with ILs, asevidenced by the formation of a stable, composite material containingthe polymer with ˜25 wt % of the IL, [C₂ mim][Tf₂N], which isstoichiometrically equivalent to one additional “free” cation-anion pairper two cation-anion pairs within/associated to the original polymerbackbone. Upon addition of the IL, the polymer material becomes morepliable and optically cloudy (FIG. 1), which can be indicative ofsupramolecular ordering, and validating the hypothesis that ionicpolyimides can accommodate significant quantities of “free” ILs withintheir structures and remain mechanically stable solids.

It will be appreciated that variants of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be combined intomany other different systems or applications. Various presentlyunforeseen or unanticipated alternatives, modifications, variations, orimprovements therein may be subsequently made by those skilled in theart which are also intended to be encompassed by the following claims.

What is claimed is:
 1. A composition, comprising an ionic polyimidehaving the formula:

wherein, Y and Z are, independent of one another, selected from thegroup consisting of null, hydrogen, halogen, hydroxyl, carbonyl, O, S,SO₂, cyano, C(CF₃)₂; substituted or unsubstituted C₁₋₂₀ alkyl,substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or unsubstitutedC₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀ heteroalkyl,substituted or unsubstituted C₂₋₂₀ heteroalkenyl, substituted orunsubstituted C₂₋₂₀ heteroalkynyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted heterocycloalkyl, substitutedor unsubstituted aryl, and substituted or unsubstituted heteroaryl; L¹and L² are selected from the group consisting of branched and unbranchedalkyl, alkenyl, and alkynyl groups having 1 to 12 carbon atoms,substituted or unsubstituted aryl, and substituted or unsubstitutedheteroaryl, and mixture there of; Q is an ionized heteroaryl; A is ananion; and n is an integer from 1 to 100,000.
 2. The composition ofclaim 1, wherein Q is selected from the group consisting of substitutedor unsubstituted pyrazolium substituted or unsubstituted pyridinium,substituted or unsubstituted pyrazinium, substituted or unsubstitutedpyrimidinium, substituted or unsubstituted pryidazinium, substituted orunsubstituted piperidinium, substituted or unsubstituted pyrrolidinium,substituted or unsubstituted indolizinium, substituted or unsubstitutedisoindolium, substituted or unsubstituted indolium, substituted orunsubstituted indazolium, substituted or unsubstituted imidazolium,substituted or unsubstituted oxazolium, substituted or unsubstitutedtriazolium, substituted or unsubstituted tetrazolium, substituted orunsubstituted thiazolium, substituted or unsubstituted purinium,substituted or unsubstituted isoquinolinium, substituted orunsubstituted quinolinium, substituted or unsubstituted phthalazinium,substituted or unsubstituted quinooxalinium, substituted orunsubstituted phenazinium, and substituted or unsubstitutedmorpholininium.
 3. The composition of claim 1, wherein Q is substitutedwith a functional group selected from the group consisting of alkyl,halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino,carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl,sulfo-oxo, sulfonyl, sulfone, sulfoxide, and thiol.
 4. The compositionof claim 1, wherein Q is imidazolium.
 5. The composition of claim 1,wherein A is selected from the group consisting of chloride, bromide,iodide, nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonamide,hexafluorophosphate, tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, and tosylate.
 6. The composition ofclaim 1, wherein Y and/or Z is a substituted or unsubstitutedtriptycene.
 7. The composition of claim 1, wherein the ionic polyimideis selected from the group consisting of:

wherein n is an integer from 1 to 100,000.
 8. The composition of claim1, wherein n is an integer from 10 to 5,000.
 9. The composition of claim1, further comprising an ionic liquid having the formula:

wherein, R¹, R², R³, R⁴, and R⁵ are, independent of one another,selected from the group consisting of hydrogen, branched or unbranchedC₁₋₁₂ alkyl, branched or unbranched C₂₋₁₂ alkenyl, and branched orunbranched C₂₋₁₂ alkynyl; and A¹ is an anion.
 10. The composition ofclaim 9, wherein A and A¹ are independently selected from the groupconsisting of chloride, bromide, iodide, nitrate, dicyanamide, acetate,bis(trifluoromethane)sulfonamide, hexafluorophosphate,tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, and tosylate.
 11. The composition ofclaim 9, wherein the ionic liquid is 1-ethyl-3-methylimidazoliumbis(trifluoromethane)sulfonamide.
 12. The composition of claim 11,wherein the ionic polyimide is selected from the group consisting of:

wherein n is an integer from 1 to 100,000.
 13. The composition of claim9, wherein n is an integer from 10 to 5,000.
 14. A method for capturingcarbon dioxide from a gas stream, comprising: feeding the gas streamthrough a membrane, wherein the membrane comprises an ionic polyimidehaving the following structure:

wherein, Y and Z are independent of the other, are selected from thegroup consisting of null, hydrogen, halogen, hydroxyl, carbonyl, O, S,SO₂, cyano, C(CF₃)₂; substituted or unsubstituted C₁₋₂₀ alkyl,substituted or unsubstituted C₂₋₂₀ alkenyl, substituted or unsubstitutedC₂₋₂₀ alkynyl, substituted or unsubstituted C₁₋₂₀ heteroalkyl,substituted or unsubstituted C₂₋₂₀ heteroalkenyl, substituted orunsubstituted C₂₋₂₀ heteroalkynyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted heterocycloalkyl, substitutedor unsubstituted aryl, substituted or unsubstituted triptycene, andsubstituted or unsubstituted heteroaryl; L¹ and L² are selected from thegroup consisting of branched and unbranched alkyl, alkenyl, and alkynylgroups having 1 to 12 carbon atoms, substituted or unsubstituted aryl,and substituted or unsubstituted heteroaryl, and mixture there of; Q isan ionized heteroaryl; A is an anion, and n is an integer from 1 to100,000.
 15. The method of claim 14, wherein Q is selected from thegroup consisting of substituted or unsubstituted pyrazolium substitutedor unsubstituted pyridinium, substituted or unsubstituted pyrazinium,substituted or unsubstituted pyrimidinium, substituted or unsubstitutedpryidazinium, substituted or unsubstituted piperidinium, substituted orunsubstituted pyrrolidinium, substituted or unsubstituted indolizinium,substituted or unsubstituted isoindolium, substituted or unsubstitutedindolium, substituted or unsubstituted indazolium, substituted orunsubstituted imidazolium, substituted or unsubstituted oxazolium,substituted or unsubstituted triazolium, substituted or unsubstitutedtetrazolium, substituted or unsubstituted thiazolium, substituted orunsubstituted purinium, substituted or unsubstituted isoquinolinium,substituted or unsubstituted quinolinium, substituted or unsubstitutedphthalazinium, substituted or unsubstituted quinooxalinium, substitutedor unsubstituted phenazinium, and substituted or unsubstitutedmorpholininium.
 16. The method of claim 14, wherein Q is substitutedwith a functional group selected from the group consisting of alkyl,halogen, alkoxyl, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino,carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl,sulfo-oxo, sulfonyl, sulfone, sulfoxide, and thiol.
 17. The method ofclaim 14, wherein Q is imidazolium.
 18. The method of claim 14, whereinA is selected from the group consisting of chloride, bromide, iodide,nitrate, dicyanamide, acetate, bis(trifluoromethane)sulfonamide,hexafluorophosphate, tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, and tosylate.
 19. The method of claim14, wherein Y and/or Z is a substituted or unsubstituted triptycene. 20.The method of claim 14, wherein the ionic polyimide is selected from thegroup consisting of:

wherein n is an integer from 1 to 100,000
 21. The method of claim 14,wherein n is an integer from 10 to 5,000.
 22. The method of claim 14,wherein the membrane further comprises an ionic liquid having theformula:

wherein, R¹, R², R³, R⁴, and R⁵ are, independently of each other,selected from the group consisting of hydrogen and branched andunbranched alkyl, alkenyl, and alkynyl groups having 1 to 12 carbonatoms; and A¹ is an anion.
 23. The method of claim 22, wherein A and A¹are independently selected from the group consisting of chloride,bromide, iodide, nitrate, dicyanamide, acetate,bis(trifluoromethane)sulfonamide, hexafluorophosphate,tetrafluoroborate, sulfate, phosphate,tris(perfluoroalkyl)trifluorophosphatemesylate, aluminum chloride,thiocyanide, mesylate, triflate, and tosylate.
 24. The method of claim22, wherein the ionic liquid is 1-ethyl-3-methyl-imidazoliumbis(trifluoromethane)sulfonamide.
 25. The method of claim 24, whereinthe ionic polyimide is selected from the group consisting of:

wherein n is an integer from 1 to 100,000.
 26. The method of claim 22,wherein n is an integer from 10 to 5,000.
 27. The method of claim 14,wherein the gas stream is a flue gas or post-combustion stream.